Trisazo urea dyestuffs



l atentetl Feb. 3,

TRISAZO UREA DYESTUFFS Otto Kaiser, Basel, Switzerland, assignor to the firm Society of Chemical Industry in Basle,

Basel, Switzerland Io Drawing. Application March 24, 1943, Serial No. 480,371. In Switzerland April 2, 1942 4 Claims. (01. 260-173) 1 It has been found that the trisazo dyestuffs of the general formula HOsS are very valuable products. In this general formula R1 stands for a benzene nucleus which contains an OH-group and a carboxyl group in orthoposition to this OI-I-group in addition to, possibly, other substituents, R2 stands for an aromatic radical of the benzene or of the naphthalene series which is derived from so-called middle components, one i stands for a hydrogen atom and the other 25 for a member of the group consisting of a hydrogen atom and a sulionic acid group, two ms stand for hydrogen atoms and one :2: stands for an atom grouping ,aqp

which atom grouping is characterized by the presence of a benzene nucleus carrying a COOI-I- group in ortho-position to a OI-I-group, and in which the --NI-I-group is linked to a carbonyl group or to the carbon atom of a atom grouping, which atom grouping belongs to a heterocyclic compound of which the heterocyclic ring consists of six members which consist themselves of three to four carbon atoms and two to three nitrogen atoms, and contains the said atom grouping at least twice and not more than three times, and in which formula the carbonyl group or the heterocyclic residue is linked to the benzene nucleus carrying the OH-group and the COOH-group by a bridge consisting of at least one nitrogen atom.

The dyestuffs explained in the foregoing formula may also be interpreted as follows:

in which R1 stands for a benzene nucleus which carries as substituents at least one OI-I-group and a carboxyl-group in ortho-position to this Ol-I-group, R2 stands for an aromatic nuclei selected from the group consisting of benzene and naphthalene nuclei, and in which nucleus the N=N-groups stand in 1:4-position to one another in which formula one it stands for a hydrogen atom and the other t for a member of the group consisting of a hydrogen atom and a sulfonic acid group, in which formula further two ms stand for hydrogen atoms. and one :0 stands for an atom grouping z-N-A-N-B i i wherein B represents an atom grouping which is characterized by the presence of a benzene ring which carries as substituents at least one OH- group and a carboxyl group in ortho-position to said OH-group, 2 stands for a member selected from a single bond and a group wherein one 1) stands for a hydrogen atom and the other 12 for a group which is linked with the group to the naphthalene component, and wherein finally A stands for an atom grouping selected from the group consisting of the carbonyl group and a heterocyclic atom grouping whose heterocyclic ring consists of six members which consist themselves of three to four carbon atoms and two to three nitrogen atoms and contains the atom grouping gN" -c to the carbon atom of which the IT] H groups are linked at least twice and not more than three times.

Such trisazo dyestufis correspond for example to the general formula inwhich atomgrouping the benzene'nucleus carries as'substituents at least onerOH-group anda carboxyl group :in :ortho-position to said OH- roup, z-"stands for a member selected from a single bond andzgroup wherein one vstands for a hydrogen atom and the other 1) for a j group which is linked with the group to the naphthalene component, and wherein finally A stands for an atom grouping selected from the group consisting of the carbonyl group and of a heterocyclic atom grouping whose heterocyclic ring consists ofsix members which contwo to three nitrogen-atoms and contains the atom grouping ksalts, especially copper salts.

4 roups are linked at least twice and not more than three times.

All these dyestuffs are characterized by a pronounced aflinity for cellulose or regenerated cellulose, for example for textiles consisting of or containing such materials, for instance mixtures of cotton and artificial fibers from regenerated cellulose or regenerated cellulose delustred by means of inorganic pigments, or mixtures of wool and. such artificial fibers. The new dyestuffs dye these materials grey to blue-grey and green or -Q ve-e. nt

wet fastness properties -.of lthezdyeings can be essentially enhanced by after-treatment with metal This metallization can be eiiected simultaneously with the dyeing.

The newitrisazo dyestuffs are obtained accordingtoithemethods -lmown for the manufacture of such-products.

'(A) Theylcan he obtained for example by diazotizing disazo-dyestuffs of the general formula series which is derived from so-called middle comr sist themselves of three to four-carbon atomsand ponents, and coupling with amino-hydroxynaphthalene-sulfonic acid derivatives,corresponding to l e erar g mu a methylbenzene, l-amino-Z-methoxy-benzene; l-

amino 3 methoxybenzene, l-amino-B-methylbenzene, 1-amino-2:5-dimethylbenzene, l-aminobenzene and the like. g

The: starting disazo -zdy.estufis .ofitheabovevchar,

' -acterized .genera1 sformula :may :be prepared in known manner: Withaidof: the indicated starting "materials. iii "(the :middle component does not easily: couplezwi-tlr the.:diazotizedsalicylictacidode- The dastness to light and the rivatives or with the diazotiz'ed monoazo-dye stuffs, it is advantageous to use them in the form of the corresponding w-methane-sulfonic acids; the dyestufis thus obtained are then saponified prior to the diazotization.

Compounds of the general formula HOsS- 1 in which 1r has the meaning indicated above include such aminonaphthalene derivatives in which :0 and the symbol explained in the first paragraph of the specification stand for an atom grouping -n-K-1IIB halogen at least twice and not more than three times.

Such compounds are obtained for example by linking amino hydroxynaphthalene sulionic acids of the general formula in which two ys stand for a hydrogen atom each, and one 1 for an NHz group, with the aid of compounds having at least two mobile halogen atoms, such as phosgene,- the dichloride of terephthalic acid, or also heterocyclic compounds in which the heterocyclic ring consists of six members which consist themselves of three to four carbon atoms and two to three nitrogen atoms,- nor more than two nitrogen atoms being adjacent, and which contain the atom grouping C...- u, h

halogen at least twice and not more than three times, with amino-hydroxybenzene-carboxylic acids, in which the carboxyl group stands in ortho-position to the OH-group and wherein any mobile halogen atoms which may still be present after linking has been effected can be exchanged, if desired by the reaction with compounds having mobile hydrogen atoms, such as ammonia, primary amines such as mono-methylamine, monoethanol-amine, aniline, 1 -amino-4i-hydroxyl;uen' zene-3-carboxylic acid and the like.

As heterocyciic compounds of the above characterized kind having at least two mobile halogen atoms there come into question for example phosgene, oyanuric chloride, cyanuric bromide, di-' chloroquinazoline, tribromopyrimidine, dichloro methyl-pyrimidine, 1:3-dichloro-5-phenylor -5- methyltriazine and the like.

Further representatives of this class of compounds are obtained if instead of the amino-hydroxynaphthalene-sulfonic acid of the already explained formula HORS y or the amino-hydroxybenzene-carboxylic acids used as startingmaterials for the radical -N-A a there are used such derivatives of these compounds in which the amino group is acylated by an aminoaroyl group or by an aminoaryl-car-- bamic acid group or substituted by a heterocyclic residue of the just characterized kind, in-which further at least one mobile halogen atom has been replaced by an arylamino group which contains still a primary, aromatically bound amino group besides the amino group which has reacted with the halogen atom,

Thus there are obtained compounds such as i Hoes- -(I.3N OH COOH COOH I on s coon t a w n N n l l t it t' N nms- COOH i H O OH (B) The dyestufis of the present invention can be further obtained by coupling the diazo-compounds of the disazo-dyestufis of the general for mula in which R1. R2 and the two is have-thealread in which two ys stand for hydrogen atoms and one stands for a primary amino group or for an amino group which is substituted by an acid radical which contains itself an aromatically bound primary amino group. When coupling is complete, the amino group is converted into the radical .1: which has also been explained above, by linking the trisazo-dystufis thus obtained with the aid of compounds described in column 5 of this specification having at least two mobile halogen atoms with such compounds free from azochromophores and which contain on the one hand a primary amino group. and on the other hand a benzene nucleus whichcontains an OH,- group and. a COOH-group in ortho-position to this .OI-I-group.

Representatives of the .ccmpOunds carrying on the one hand an aminogroup and onthe other hand an QI-I-group which stands-in ortho-positierto a carboxyl group, may consist ofaminophcnols which contain a carboxylgroup in orthoc position to the OH-group. Suchcompounds have been enumerated for example inieolumn 4, lines 50-57 of the present specification. More complicated compounds may also be used, for example the reduced condensation products from nitrated aromatic carboxylic acid chlorides and the just named aminophenol-carboxylic acids. Condensation products may also be used which are obtained by linking the cited aminophenol-carbom ylic acids with aromatic compounds which besides a primary amino group contain asecond primary amino group or an atom grouping convertible into such a group, with the aid of the compounds described in column 5, lines 53-62 and'column 6 lines 1-7 of the present specification containing at least two mobile halogen atoms, and after effecting the linkage converting the convertible atom grouping into an amino group. The amino groups in azo-dyestufis of, the general formula and one y stands for .an' amino group, are thus converted into the alreadyexplained radical :0

Hots

sat-sac which-may cor espond for exem leto the-flit??? meter-mules a and the like (ct, in this connection the formulas incolumn-fi of this specification).

I The followingexamples illustrate the invention; but are not to be regarded as limiting it in, any way, the parts being by weight: 7

Example 1 23.3 parts of 1=amino-3-carboxy-4-hydroxybenzene-fi-sulfonic acid are ,diazoti'zed in usual mariner 111150 parts of water and coupled at 0 in the presenceof sodium acetate'with 13.7 parts of 1-amino-3-rnethy1-6-methoxybenzene which have been dissolved in 10 parts of concentrated hydrochloric acid and 40 parts of water. The monoazodyestufi which separatesis brought into solution with aqueous caustic soda solution, mixedwith 6.9. partsof sodium nitrite in anaqueous solution of 2 5 per cent. strength, and the whole is allowed to run into-a mixtureof 200 parts of ice water and 50 parts of concentrated hydrochloric acid. When the diazotization which has been carried out at'0-.5, C. is complete, the diazo compound which has separated with common salt is sucked off and coupled with 22.3 parts of 1-naphthylamine-fiesulfonic acid which as sodium salt have been dissolved in 200 parts of water. 20 parts of sodium acetate are strewn in during 1 oupling nd thep o u isv separat d after so e time with common salt. It is brought into solu; tionwit s m austic soda s lu on, mixed ith 6-9 parts, o sodium nit n a solution .of .25 pe cent-st n h, nd this m xture isfurther diametized at -0. with a ixture of 200 parts ofxiee water-a d 50 par of onc ntrated hydrochloric ac d, he diaze c mp u d w h hasseparait d sthenmixed a solution alkaline w thsod um a bonate wit 41.8 parts of u ea from quimolecular proportions of z-amino-s-hydroxynaphthalene-7-sulionic acid and 1-amino-3-carboxy- 4-hydroxybenzene prepared in known manner with ph s ne.

When coupling is complete, the dyestufi' of the formula is separated and dried. It is a dark powder which of water. 20 parts of sodium acetate are strewn dyes cotton in a feebly alkaline bath in the presin during coupling and the product is separatence of copper sulfate in sodium tartrate reddish ed after some time with common salt. It is grey tints which are fast to washing. brought into solution with some caustic soda so- In this example the 1-amino-3-carboXy-4-hy- 5 lution, mixed with 6.9 parts of sodium nitrite droxybenzene-B-sulfonic acid can be replaced by in a solution of 25 per cent. strength, and this the l-amino 3 carbcxy-ei-hydroxy-benzene-6- mixture is further diazotized at 15 C. with. a sulfonic acid or by the l-aminc-Z-hydrowbenmixture of 200 parts of ice water and 50 parts of zene-3-carboxy-S-sulionic acid. The l-aminoconcentrated hydrochloric acid. The diazo com- 3-methyl-6-methoxybenzene can also be replaced 10 pound which has separated is then mixed in a by the 1-amino-3-methylbenzene, the l-aminosolution alkaline with sodium carbonate with 2:5-dimethyl-benzene, the 1-amino-2z5-dimeth- 53.3 parts of urea from equimolecular quantioxybenzene, the 1-amino-3-acetyl-aminobenzene, ties of 2-(3'-aminobenzoylamino)-5-hydroxythe 1-amino-2-meth0xybenzene (in the form of naphthalene-'Y-sulfonic acid and 1-amino-3-carits w-methane-sulfonic acid) or by the l-aminobosyi-hydroxybenzene prepared in known man- 2-methoxy-5-acetylamino-benzene. The l-naphher with phosgene. thylamine-G-sulfonic acid can be replaced by the When coupling is complete, the dyestufi' of the l-naphthylamine-I-sulfonic acid or also by the formula HO N=N N=N N=N C i i i 000E soiu- *o0 N-00-N-QOH SOQH SOKH COOH technical mixture of the l-naphthylamine-G- and is separated and dried. It is a dark powder which the 1-naphthylamine-'7-sulfonic acid. The dyes cotton in a feebly alkaline bath'in the presconnecting link CO can be replaced by a triazine ence of copper sulfate and sodium tartrate greenradical or a phenyltriazine radical or by a quinish blue tints which are fast to washing. azoline radical. Finally, the derivative of the A similar dyestuif is formed when replacing the 2-amino-5-hydroxynaphthalene-'I-sulfonic acid 2-(3'-aminobenzoylamino) 5-hydrcxynaphthacan also be replaced by a derivative of the 2-ami- 1ene-7 -sulfonic acid by the 2-(4-aminobenzoylno-8-hydroxynaphthalene-fi-sulfonic acid or by amino)-5-hydroxynaphthalene-7-sulfonic acid. a derivative of the I-amino-S-hydroxynaphtha- The 1-naphthylamine-'7-sulfonic acid can also lene-l-sulfonic acid. be replaced once or twice by the l-naphthyl- Further dyestuiis are for example those of the amine-G-sulfonic acid or c by a technical mixformulas ture of the two acids. Besides this, reference is H000 OH omo OH I I l I N Eli ON=NQN=N N=N NHC/ E-NQOH sour 011, 503K coon 1100c OH HO N= N=N N=N n i SOaH N-(J-NQOH 803E coon Example 2 made to the explanations in the last paragraph 15.3 parts of 1-amino-3-carboXy-4-hydroxyi Egarnple 1 whmh apply l here ma mubenzene are diazotized in usual manner and an Exampz 3 coupled at 0 C. in the presence of sodium ace- 09 e tate with 22.3 parts of l-naphthylamina-Y-wl- 15.3 parts of 1-amino-3-carboxy-4-hydroxyionic acid which as sodium salt have been disbenzene are diazotized in usual manner and solved in 200 parts of water. The monoazo-dyecoupled at 0 in the presence of-sodium acetate stuff which separates is brought into solution with 22.3 parts of 1-naphthylamine-7-sulionic with aqueous caustic soda solution, mixed with acid which as sodium salt have been dissolved in 6.9 parts of sodium nitrite in an aqueous solu 209 parts of water. The monoazo-dyestuff which tion of 25 per cent. strength, and the whole is separates is brought into solutionwith aqueous allowed to run into a mixture of 200 parts of ice caustic soda solution, mixed with 6.9 parts of water and parts or" concentrated hydrochloric n sodium nitrite in an aqueous solution of 25 per acid. When the diazotization which has been carcent. strength, and the whole is allowed to run ried out at 0-5 C. is complete, the diazo co'ninto a mixture of 200 parts of ice water and 50 pound which has been separated with common parts of concentrated hydrochloric acid. When salt is sucked oii and coupled with further 22.3 the diazotization which has been carriedout at parts of 1-naphthylamine-7-sulfonic acid which 0-5? C. is complete, the diazo compound which as sodium salt have been dissolved in 200 parts 0 has been separated with common salt is sucked .ica'l. Besides this, reference is made to the ex- 11 oil and coupled "with "13-37 parts .:of l-amino-B- *methyl-fi-methoxybenzene which :have been dissolved in parts of concentrated hydrochloric acid and 40 partsof water. parts of sodium acetate are strewn in dur-ingcouplingand the product is separated after some time with common salt. It is'brought into solution with some caustic soda solution, mixed with 6.9 parts of sodium nitrite in a solution of per cent. strength, and this mixture is further diazot'ized at 15 C. with a mixture of Z'OO-parts-of ice water and '50 parts of concentrated hydrochloric acid. The suction-filtered-diazosolution is then mixed 'in a solution alkaline with sodium carbonate with 65 partsof urea from l-mol.=of'2-('4-amino benzoylamino) 5 hydroxynaphthalene -7-sulfonic acid and 1 mol. of 4-( 4="--aminobenzoylamino) -1 hydroxybenzene 2 carboxylic acid which has been prepared in known manner.

When coupling is complete, the dyestuff of the 20 formula I 12 amples 1 andand to 'those inthe introduction from which numerous'modifications in'themanu- =facture of'the dyestufi of this example can be gathered.

. Example 4 at this temperature. solution of .2 .partsof crystallized coppersulfatezzand 2.5 parts :of water :of tartaric acid in 100 parts "which has :beenzneutralized withzcaustic sodazsolutionis added :tothe dye-bath and the cotton is treated for /2 hour at 95 C. The cotton is rinsed as usualand dried. It is dyed fastreddish grey tints.

s i H I H0O.

*is'separatedand dried. It is a dark powderwhich dyes cotton in a feebly alkaline bathin the pres- The dyestuffs of the'present invention can be used also for .dyeing mixed fabrics, :for {example ence of cqpper ulfate n Sodium mrtmtegrey fabrics consisting of wool and :viscose cellulose tintswhicharefast to washing.

Here, too, the middle components can "be rep aced by those indicated in Example 1. The para-nitrobenzoyl-chloride used 'for the manufacture of the urea-like azo-components can -he replaced by one or /2 mols. of meta-nitrobenzoylchloride. Furthermore, the'CCl-groupof'the urea radical can be replaced by a triazine radicalfby -wool. In such cases-it is preferable to :dye :inra.

neutral bath in the presence ofzsodiumiandpotassium chromate.

Further examples of dyestufis made in :accordance with the invention are given in the following table, in which the dyestuffs are of the formula Eli- N=N1-RZN=N--R3QN=NY X-Z and the components of each dyestufi are {listed a phenyl-triazineradical or by a-. g-uinazo1ine rad- --in the .columns headedR1, R2, R3, Y, X and Z:

Table R; Ra R: Y X Z 1 l-aminol-hydroxyl-amino-2-methoxyl-aminonaphtha- *Z-amino-B-hydroxy- I l-amino-4-hydroxybenzene- 5-sulfo-3- 5-methy1benzene. lenef-7-sulfonic naphthalene-(i-suh -CN CO benz,ene-3-carboxcarboxyllc acid. acld. ionic acid. A I ylic acid.

2 do .do -do 2-amino-5-hydroxy- ...do D0.

naphthalene-7-su1- ionic acid. .13., .l-aminoA-hyd roxyleammonaphthalene. .;do do .do D0- be11zenc-3-cerbox-' I .ylicaci'd. 4 do l-aminonaphthalene- -.do -do 0:0 -D0.

7-su1fomc acid. 6 ...--do il'amlnonaphtl alenel-aminonaphtha- 2-amino-8'-hydroxy- D0.

6-su1ionicac1d. lene. naphthalenet-suliG"N- CO tonic acid. I] I 0 1H ,6 do Jeminonaphthalenedo do .do D

7-sull'onic acid. T -.do do 'l-aminonaphtha-v 2-(4'-aniinophenyl- 'do D0.

. lene -7 -su1fcnic amino)-8-l1ydroxy- 'flCld. naphthalene'fi-sulionic acid. 8 do .l-ammonephthaleno. .do 2-amino-5-hydroxy- N 1.-hydr0Xy- -amin0-. na hthalene-7-sulnitrobenzene'-6:car-

fomcacld. 3 ('J (13-- "boxylicacid. N\

HNCuHn planations in the last paragraph Ufeachhffilm The dyestufis 1, 4 and 8 of theforegoing table correspond to the following formulas:

a or"; ooze:

SOzH CH: $03K HOzS oH- N=l N=N N=:-

1 no 0 o S0211- H035 SOaH Hois- What I claim is: 1. The trisazo-dyestuffs of the general formula wherein R1 stands for a benzene nucleus which contains as substituents at least one OH-group and a carboxyl group in ortho-position to this OH-group, R2 stands for an aromatic nucleus selected from the group consisting of benzene and naphthalene nuclei and wherein the --N=N- groups stand in 1:4-position to one another, in which formula one t stands for a hydrogen atom and the other t for a member of the group consisting of a hydrogen atom and a sulfonic acid group, wherein further two :ns stand for hydrogen atoms and one :2: stands for an unsulfonated atom grouping COOH 1 BOON: 8

SOaH

wherein R1 stands for a benzene nucleus which contains as substituents at least one OH-group rrwgrrck HOH on OOOH wck which products dye the cellulose fibers grey to blue-grey and green-grey tints, the wet fastness properties of which can be improved by aftertreatment with compounds yielding copper.

3. The trisazo-dyestufis of the general formula on 1: =N N=N 1 8 11 wherein two 32's stand for hydrogen atoms and one :1: stands for the atom grouping OOH 4. The trisazo-dyestufi of the formula rrrQ H O H COOH OTTO KAISER.

(References on following page) .The "ml lowing v references are. .of. record "in the v REFERENCES CITED Anderau Jan. 6, '1942 Number FOREIGN PATENTS Couri'tri' "'DaJ-te Germany "Ju 1y 11, 1929 Germany Aug. 9, 1934 Great Britain Aug. '24, 1938 France Jan. 28, 1929 

